US3960569A - Diffusion transfer color film unit with hydroxy substituted alkylene amino development accelerators - Google Patents

Diffusion transfer color film unit with hydroxy substituted alkylene amino development accelerators Download PDF

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US3960569A
US3960569A US05/525,431 US52543174A US3960569A US 3960569 A US3960569 A US 3960569A US 52543174 A US52543174 A US 52543174A US 3960569 A US3960569 A US 3960569A
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light
layer
group
film unit
image
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Yoshiaki Ono
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/42—Structural details
    • G03C8/44—Integral units, i.e. the image-forming section not being separated from the image-receiving section
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C8/00—Diffusion transfer processes or agents therefor; Photosensitive materials for such processes
    • G03C8/02—Photosensitive materials characterised by the image-forming section
    • G03C8/04—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals
    • G03C8/045—Photosensitive materials characterised by the image-forming section the substances transferred by diffusion consisting of inorganic or organo-metallic compounds derived from photosensitive noble metals with the formation of a subtractive dye image

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  • the present invention relates to a method for rapidly obtaining a diffusion transfer color image with high contrast using a dissolution-physical development system.
  • diffusion transfer color photographic method in which a silver halide emulsion layer is used as a light-sensitive element and an imagewise distribution of diffusible dye image-forming materials such as diffusible dyes formed as a result of the development of the exposed silver halide emulsion layer is allowed to diffuse into another layer and fixed there to form transferred dye images is well-known.
  • a method for obtaining a transferred dye image by using an aromatic primary amino color developing agent and a ballasted coupler capable of coupling with an oxidation product of the color developing agent, and several chemical means for obtaining a positive image distribution of diffusible dyes by using a negative-type silver halide emulsion as a light-sensitive element are known.
  • the transfer of dye images from a light-sensitive element comprising a support having superposed thereon a plurality of emulsion layers having associated therewith diffusible dye-providing materials for subtractive color reproduction, to a common image-receiving layer is also known.
  • some type of image-reversing optical mechanism is necessary for obtaining a color image corresponding to a photographed object.
  • the present invention comprises a film unit having this image-reversing mechanism using a dissolution-physical development system.
  • a negative-type silver halide emulsion layer containing a ballasted compound capable of reacting with an oxidation product of an aromatic primary amino color developer to provide a non-diffusible compound (i) a light-insensitive layer adjacent the silver halide emulsion layer, containing a ballasted coupler and physical development nuclei, with the ballasted coupler being capable of reacting with an oxidation product of the developer to provide a diffusible dye; and (iii) an aromatic primary amino color developer as a processing solution or a precursor thereof in a light-sensitive element and a solvent for silver halide, the precursor being capable of providing the developer as a result of hydrolysis with a processing composition; are required.
  • the diffused silver complex salt in order to obtain an instant photograph in a short time, it is desirable for the diffused silver complex salt to rapidly liberate a diffusible dye with a positive image distribution with the help of physical development nuclei, a ballasted coupler capable of reacting with an aromatic primary amino color developing agent to release a diffusible dye, an alkali in a processing solution and an aromatic primary amino color developing agent, thus rapidly releasing a diffusible dye with a positive image distribution.
  • a silver-complexing agent acts before the silver halide is completely negative-developed, and hence the agent acts not only on the silver halide located at the unexposed areas to form a silver complex salt but also on the silver halide located at the exposed areas to similarly form a silver complex salt, the complex salt diffusing into a physical development nuclei-containing layer.
  • the resulting positive image exhibits a characteristic curve in which the minimum density (Dmin) at a toe area is high and both the sensitivity and contrast are low. Therefore, only an unsatisfactory image of low practical value can be obtained. This characteristic cannot be markedly improved by changing the amount of developing agent or silver-complexing agent.
  • This processing solution must be retained in a rupturable container and must be unified with a film unit so that a number of film units can be stacked as compactly as possible in a film cassette for use in a camera. Therefore, the amount of the processing solution used must be as small as possible. Otherwise, a thick film cassette would be necessaryy, resulting in the production of a compact camera being impossible. Also, if a processing solution with low developing power must be spread thickly, the amount of water necessarily becomes great, and hence a thickening agent must be used in a large amount.
  • An object of the present invention is to accelerate the progress of developing a negative emulsion and to increase the rate of dissolving silver halide by a solvent for silver halide, by adding the compound of the present invention to a development-processing solution, and to accelerate the rate at which a diffusible dye released from a positive layer is diffused into and fixed in an image-receiving layer, by increasing the activity of a developer and making the necessary thickness of a processing solution as thin as possible and reducing the amount of a thickening agent used. These are necessary for attaining color diffusion transfer with rapidity and high sensitivity.
  • Another object of the present invention is to markedly reduce the undeveloped silver halide grains at the exposed areas (so-called "dead grains"). This can be attained by adding the compound of the present invention, whereby the rate of developing a negative emulsion is enhanced.
  • a solvent for silver halide such as sodium thiosulfate dissolves even these dead grains to form a silver complex salt, which salt then moves into a positive layer (a layer containing physical development nuclei and a ballasted coupler capable of releasing a diffusible dye) and causes physical development to form a dye. This dye is then diffused into an image-receiving layer and fixed there. Thus, a positive image with a serious amount of stain is formed. Therefore, it is necessary to effect development as strongly as possible so as to remove these dead grains.
  • a positive layer a layer containing physical development nuclei and a ballasted coupler capable of releasing a diffusible dye
  • a further object of the present invention is to prevent silver halide at the exposed areas from being dissolved prior to development to diffuse into a positive layer (a layer containing physical development nuclei and a ballasted coupler capable of releasing a diffusible dye).
  • a positive layer a layer containing physical development nuclei and a ballasted coupler capable of releasing a diffusible dye.
  • Such diffusion at the exposed areas would result in unfavorable physical development occurring and in releasing a diffusible dye which would diffuse into an image-receiving layer and be fixed there to form a large amount of stain.
  • This object is attained by accelerating the negative development of the exposed areas, whereby a solvent for silver halide is allowed to act after the completion of the negative development.
  • the present invention comprises a diffusion transfer color film unit of the dissolution-physical development system
  • a light-sensitive element comprising a support having thereon at least one light-sensitive layer unit comprising (i) a negative-type silver halide emulsion layer containing a ballasted compound capable of reacting with an oxidation product of an aromatic primary amino color developing agent to provide a nondiffusible compound and (ii) an adjacent layer containing physical development nuclei and a ballasted coupler capable of reacting with an oxidation product of an aromatic primary amino color developing agent to provide a diffusible dye;
  • an image-receiving element comprising a support having thereon an image-receiving layer capable of fixing diffusible dyes released from the light-sensitive element;
  • a rupturable container which retains an alkaline processing composition and capable of releasing the contents by the action of pressure-applying members;
  • an aromatic primary amino color developing agent in the processing composition or a precursor thereof which provides, upon hydrolysis with the processing composition, the aromatic primary amino color developing agent in the light-sensitive element, and a solvent for silver halide and
  • the diffusion transfer color film unit containing at least one compound represented by the following general formula (I) or (II); ##EQU3## wherein R 1 and R 2 each represents an alkylene group having 1 to 4 carbon atoms; and R 3 represents a hydrogen atom, an amino group, an alkyl group having 1 to 4 carbon atoms or an aminoalkyl group having 1 to 4 carbon atoms; and ##EQU4## wherein R 4 and R 5 each represents an alkylene group having 1 to 4 carbon atoms; and R 6 represents a hydrogen atom, an amino group, an alkyl group having 1 to 4 carbon atoms or an aminoalkyl group having 1 to 4 carbon atoms.
  • FIG. 1 is a cross sectional view showing a light-sensitive element, a image-receiving element and a processing composition container which can be used in the present invention.
  • FIG. 2 is a perspective view of one embodiment of a film unit of the present invention, wherein FIG. 2a is as viewed from the light-sensitive element side and FIG. 2b is as viewed from the image-receiving element side.
  • FIG. 3 is a perspective view of another embodiment of the film unit of the present invention.
  • FIG. 4 is a cross sectional view of the film unit illustrated in FIG. 3.
  • examples of alkylene groups having 1 to 4 carbon atoms represented by R 1 , R 2 , R 4 and R 5 include, e.g., a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a 1,1-dimethylethylene group, a 2-methyltrimethylene group, etc.
  • alkyl groups having 1 to 4 carbon atoms represented by R 3 and R 6 include, e.g., a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a secbutyl group, a t-butyl group, etc.
  • Suitable aminoalkyl groups having 1 to 4 carbon atoms represented by R 3 and R 6 are, e.g., an aminomethyl group, an aminoethyl group, an aminopropyl group, an aminobutyl group, etc.
  • the light-sensitive element is imagewise exposed in a camera either directly from the opposite side to the support side or through the transparent support from the support side.
  • a processing composition is spread between the light-sensitive element and an image-receiving element in a layer form by applying a pressure to a processing composition container through pressure-applying members to rupture it, with the surfaces opposite to the supports of the two elements being disposed in a face-to-face contact with each other.
  • Each light-sensitive silver halide emulsion layer of each light-sensitive layer unit is developed in accordance with the exposure amount by the action of the development accelerator of the present invention, an alkali and an aromatic primary amino color developing agent (or the same developing agent released from a precursor contained in the light-sensitive element due to hydrolysis with the alkali), with the development accelerator, alkali and developing agent being introduced by the processing composition.
  • the development is of a negative type.
  • the color developing agent is oxidized and reacts with a ballasted coupler within the light-sensitive emulsion layer to provide non-diffusible dyes.
  • the silver halide in the light-sensitive emulsion layer at the unexposed areas is dissolved by the action of a silver-complexing agent such as sodium thiosulfate and the thus formed complex salt diffuses into an adjacent layer containing fine physical development nuclei and a non-diffusible coupler capable of producing a diffusible dye.
  • a silver-complexing agent such as sodium thiosulfate
  • the thus formed complex salt diffuses into an adjacent layer containing fine physical development nuclei and a non-diffusible coupler capable of producing a diffusible dye.
  • physical development nuclei include nuclei of noble metals such as silver, platinum, palladium, gold, rhodium, ruthenium, osmium, etc., as disclosed in U.S. Pat. No. 3,647,440 and silver sulfide, palladium sulfide, gold sulfide and the like.
  • the silver complex salt diffused from the light-sensitive emulsion layer, rapidly undergoes physical development with the help of an alkali, an aromatic primary amino color developing agent (or the same developing agent released from a precursor contained in the light-sensitive element due to hydrolysis with the alkali), physical development nuclei, the development accelerator of the present invention and a color coupler.
  • This physical development is accompanied by the oxidative coupling reaction between the ballasted coupler contained in the light-insensitive layer and an aromatic primary amino developing agent, thus a diffusible dye being released with a positive image distribution.
  • the diffusible dyes released from each light-sensitive layer unit diffuse through the light-sensitive element and through the processing solution layer and reach the image-receiving layer, where they are fixed to form a positive dye image.
  • the development in the light-sensitive element is discontinued due to the exhaustion of effective ingredients contained in the processing composition or by means of a timing mechanism for stopping development, with this timing mechanism being contained in the film unit.
  • the light-sensitive element is separated from the image-receiving element depending upon the purpose of the end use of the film unit.
  • the light-sensitive element is sometimes utilized after being subjected to a silver-removing processing or the like.
  • the compound of the present invention is effective when added in an amount of about 0.05 g to 5 g per liter of the processing solution. If the amount of the compound of the present invention is less than about 0.05 g, the effect of improving the contrast of the positive image is low, while, if more than about 5 g of the compound of the present invention is present the fog of a negative emulsion increases and the Dmin of a positive image is increased, with the Dmax being reduced, reducing the difference between the Dmax and the Dmin ( ⁇ D) in the positive image and resulting in an image having low contrast. Therefore, a preferred amount of the compound of this invention added is 0.05 to 3 g per liter of a processing solution.
  • the conventional compounds were found to be ineffective for the dissolution-physical development system.
  • the effect of the sensitizer is influenced by complicated factors before the formation of a positive image, such as the dissolving rate of silver halide, the diffusion rate of the silver complex into a positive layer, the stability of the silver complex and the activity of physical development nuclei, which is different from the black-and-white and conventional color systems.
  • the rate of dissolving the silver halide must be so adjusted that dissolution of silver halide does not precede the negative development, and the silver complex salt must possess a staability such that it is stable until the silver complex salt reaches the positive nuclei-containing layer (physical development nuclei-containing layer) and is decomposed as fast as possible in the vicinity of the nuclei contained in the positive nuclei-containing layer. Also, the activity of the physical development nuclei is not at presently clearly understood.
  • the silver complex salt is decomposed in the presence of a developing agent, an alkali and developing nuclei, silver is deposited on the nuclei and, in this occasion, an oxidation-reduction reaction occurs between the silver complex and the developing agent in which the oxidized developing agent reacts with a coupler to release a diffusible dye. It is certain that the rate of color development and the color density due to this physical development in this occasion greatly depend upon the activity of the physical development nuclei. The particle size, the surface area and the kind of the physical development nuclei are important factors.
  • the aforesaid conventional sensitizers can reduce the activity of the physical development nuclei due to adsorption on them, or they may have a poor ability for accelerating dissolution of the silver halide as well as a poor ability for accelerating the negative development.
  • the compound of the present invention is an excellent additive for a processing solution in accordance with the dissolution-physical development system, which can accelerate the negative development and, at the same time, increase the rate of positive color development.
  • diethanolamine and triethanolamine which are known as sensitizers for black-and-white and conventional color systems, exhibit no effects on accelerating development and no effects on improving contrast when applied to the dissolution-physical development system.
  • the diffusion-physical development system is a special area.
  • compounds e.g., CH 3 CH 2 CH 2 NH 2 , NH 2 CH 2 CH 2 CH 2 NH 2 , etc., as described in German Pat. O.L.S. No. 2,300,772 are known as sensitizing agents.
  • these compounds possess difficulties in that they have a strong offensive odor specific to amines and in that they possess too strong a reducing power and increase the fog of the negative emulsion, resulting in a reduction in the density of the dye images.
  • the compounds of the present invention having a hydroxy group in their molecule possess less odor have a suitably low reducing power and exhibit a suitable silver halide dissolving ability and are, therefore, excellent as an additive to a processing solution in accordance with the dissolution-physical development system.
  • the compounds of the present invention having a hydroxy group in their molecule possess less odor and possess a suitably low reducing power, they do not have the defect that even an unexposed emulsion is indiscriminately developed and they possess a suitable silver halide dissolving ability. Thus, they are excellent as an additive to a processing solution in accordance with the dissolution-physical development system.
  • diffusibility when a sufficient quantity of a substance, contained in each layer of the film unit or in the layer formed upon processing, to cause photographic effects diffuses into another layer, this substance is referred to as being diffusible, whereas a substance which diffuses only in an insufficient amount to substantially cause any photographic effects is referred to as being non-diffusible.
  • Effective ingredients rendered non-diffusible through means such as association or polymerization are sometimes referred to as being diffusion-resistant or ballasted. These terms are used in the manner conventionally employed in the color photographic field.
  • the degree or extent of diffusion is appropriately determined taking as a standard the conditions of the photographic layer into which the processing composition has permeated. More specifically, with respect to the film unit of the present invention, the extent of diffusion is appropriately determined based on the degree of diffusion in a hydrophilic colloid layer such as a gelatin layer containing an alkaline aqueous solution of a pH of about 10.
  • color sensitivity and the “absorption of dyes” are employed in their conventional manner widely accepted in subtractive color reproduction photography.
  • the present invention can also be applied to a system which contains auxiliary color-correcting means in addition to the three main colors employed in subtractive color reproduction photography.
  • the coupler which is contained in a light-insensitive layer and which provides a diffusible dye is said to be colorless in such a sense and extent that the coupler possesses no absorption of light in the light-sensitive wavelength region of the unit containing the coupler which absorption greatly reduces the sensitivity of the light-sensitive emulsion and that the processed light-sensitive element does not possess an absorption which seriously deteriorates the property of the element as a negative original for color printing.
  • the image distribution-transmitting material used in the present invention plays, in each light-sensitive layer unit, a role of transmitting information controlling the image distribution. That is, the material migrates from a negative-imagewise developed light-sensitive emulsion layer to a light-insensitive layer associated therewith and functions to cause a reduction of silver with a reversal positive image distribution corresponding to the negative image in the light-sensitive emulsion layer.
  • the image distribution-forming material can be either (i) a development product produced with a negative image distribution simultaneously with the development of the light-sensitive emulsion layer or (ii) a substance which is initially incorporated uniformly in the light-sensitive emulsion layer and, upon development of the light-sensitive emulsion layer, is consumed with a negative distribution, leaving a positive distribution of the substance which is rendered diffusible with the processing composition.
  • a positive image-forming material is incorporated which causes silver reduction of a positive image by the action of the image distribution-transmitting material or which facilitates silver reduction.
  • a method of causing the development-controlling effects of the development product from the light-sensitive emulsion to act on the adjacent, substantially light-insensitive fogged emulsion layer and a method of dissolving non-developed silver halide emulsion grains in the light-sensitive emulsion layer with a complexing agent and transferring the dissolved silver to an adjacent layer containing physical development nuclei are particularly useful for the film unit of the present invention.
  • Positive diffusion transfer dye images can be obtained by processing the light-insensitive layer provided adjacent the negative silver halide emulsion layer and containing a diffusible dye-releasing coupler and physical development nuclei, with a developer containing a solvent for silver halide.
  • Suitable techniques for forming reversal dye images utilizing physical development which can be employed are those described in U.S. Pat. No. 3,227,550, etc.
  • the ballasted couplers which provide non-diffusible dyes are compounds which contain both a coupler nucleus residue capable of reacting with an oxidation product of an aromatic primary amino color developing agent to form a dye structure and a hydrophobic residue having 8 or more carbon atoms.
  • the coupler nucleus residues can be those described in C.E.K. Mees and T. H. James, The Theory of the Photographic Process, 3rd Ed., pp. 383 ⁇ 394, Macmillan, (1966) and W. Pelz, Farbkuppler, pp.
  • the hydrophobic residue functions to reduce the solubility of the coupler in an aqueous medium or reduce the diffusibility thereof in photographic layers by the action of increasing the cohesive force between the coupler molecules or between the coupler molecule and an oily substance to thereby increase intermolecular association, or the like.
  • Useful hydrophobic residues are a straight or branched chain alkyl group such as an n-octyl group, a 2-ethylhexyl group, t-octyl group, an n-nonyl group, a triisopropyl group, a decyl group, an n-dodecyl group, a 1,1-dimethylhexadecyl group, a stearyl group, etc.; a cycloalkyl group such as 2,4-di-n-amylcyclohexyl group, etc.; an alkenyl grop such as an oleyl group, etc.; an aryl group such as a terphenyl group, etc.; a haloalkyl group such as an 8,9-dichloroheptadecyl group, a perfluorooctyl group, etc.; an alkoxyalkyl group or an alkylthi
  • hydrophobic residues can be connected to the coupler nucleus residue either directly or through a divalent linking group such as an alkylene group, an arylene group, an oxyalkylene group (-- O-alkylene-group) (e.g., an oxymethylene group, an ⁇ -oxyethylene group, an ⁇ -oxypropylene group, an ⁇ -oxybutylene group, etc.), an amido group, a carbamyl group, a sulfonamido group, a sulfamyl group, ##EQU6## etc.), a carbonyl group, a carbonyloxy group, an oxycarbonyl group, a sulfonyl group, a sulfonyloxy group, an oxysulfonyl group, or the like.
  • a divalent linking group such as an alkylene group, an arylene group, an oxyalkylene group (-- O-alkylene-group) (e.g.,
  • the hydrophobic group can be contained in the substituent positioned at the coupling site which is eliminated by the oxidation product of an aromatic primary amino color developing agent.
  • the ballasted couplers used in the present invention can contain water-solubilizing groups such as a sulfo group, a carboxy group, a sulfonamido group, etc.
  • the hydrophobic residues preferably contain about 12 to 32 carbon atoms, whereas in the so-called oleophilic protect-type couplers without such hydrophilic groups, the hydrophobic residues preferably contain about 8 to 32 carbon atoms.
  • ballasting group comprising the hydrophobic group and the linkage group particularly suitable for the ballasted couplers
  • a fatty acid amido group such as an n-lauroylamido group, a stearoylamido group, an oleoylamido group, etc.
  • a carbamyl group substituted with an alkyl or alkenyl group such as an N-laurylcarbamyl group, an N-methyl-N-stearylcarbamyl group, an oleylcarbamyl group, etc.
  • substituted aliphatic amido groups as described in U.S. Pat. Nos.
  • aliphatic amido groups substituted with an alkylaryloxy group such as an ⁇ -dimethyl- ⁇ -(3-pentadecylphenoxy)acetamido group
  • aliphatic amido groups substituted with a water-solubilizing group such as a 1-octadecenyl-succinmonoamido group, an ⁇ -sulfostearoylamido group, etc.
  • alkoxy groups such as an octadecyloxy group, etc.
  • ester groups such as a cetyloxycarbonyl group as described in U.S. Pat. Nos. 3,409,439 and 3,551,155
  • sulfamyl groups such as an N,N-dioctylsulfamyl group, etc.; and the like.
  • an ⁇ -acylacetamido residue and, particularly preferably, an ⁇ -acylacetanilido residue are useful. These residues can be connected to the above-described ballasting groups containing the hydrophobic residue in the acylamido(anilino) group and the eliminatable residue at the coupling position.
  • the above-described coupler nuclei can further be substituted with substituents such as a halogen atom, an alkyl group, an alkoxy group, an amyloxy group, a carbonyl group, a sulfo group, an alkoxycarbonyl group, a sulfamyl group, an acylamido group, a sulfonamido group, an amino group, a nitro group, a cyano group, etc.
  • substituents such as a halogen atom, an alkyl group, an alkoxy group, an amyloxy group, a carbonyl group, a sulfo group, an alkoxycarbonyl group, a sulfamyl group, an acylamido group, a sulfonamido group, an amino group, a nitro group, a cyano group, etc.
  • ballasted couplers which can be advantageously used in the present invention providing non-diffusible yellow dyes can be selected from conventionally known yellow couplers as described in Mees and James, supra, and Pelz, supra.
  • ⁇ -Benzoylacetamide couplers containing a water-solubilizing group as described in BIOS 1901, FIAT 943 and Japanese Patent Publication No. 6030/65; oleophilic ⁇ -benzoylacetamide couplers as described in U.S. Pat. Nos. 2,407,210; 2,875,057; 3,409,439; 3,551,155; 3,551,156; 3,649,276; 2,685,995; British Pat. No.
  • 1,286,411; ⁇ -pivaloylacetamide couplers as described in U.S. Pat. No. 3,265,506; and the like are particularly useful for the practice of the present invention.
  • one hydrogen atom located at the ⁇ -position of these ⁇ -acylacetamido groups can be substituted with a residue which can be eliminated as an anion, such as an arylthio group, a heterocyclic thio group, a halogen atom such as a fluorine atom as described in U.S. Pat. No. 3,277,155, a thiocyano group as described in U.S. Pat. No. 3,253,924, an acyloxy group as described in U.S. Pat. No.
  • Typical preferable yellow couplers include the following couplers.
  • nuclei for the couplers which can be used in the present invention providing magenta dyes a 5-pyrazolone residue, a pyrazolobenzimidazole residue, an indazolone residue and a 1-H-pyrazolo[3,2]-s-triazole residue are useful.
  • the 1-aryl-5pyrazolones are useful.
  • 5-pyrazolone compounds having in the 1-position an unsubstituted phenyl group or a phenyl group substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamido group, a carbamyl group, a sulfamyl group, an alkoxycarbonyl group, a cyano group, a nitro group, a carboxy group, a sulfo group, etc., and the 5-pyrazolone compounds substituted in the 3 -position with an alkyl group, an alkoxy group, an aryloxy group, an amino group (e.g., an anilino group, etc.), an acylamino group, a sulfonamido group, an ureido group, a carbamyl group, an alkoxycarbonyl group, etc., can be used with great advantage.
  • ballasted couplers which can be advantageously used in the present invention providing non-diffusible magenta dyes can be selected from those known and descirbed in Mees and James, supra, and Pelz, supra, and in the literature.
  • 1Phenyl-3-alkyl-5-pyrazolone couplers containing a water-solubilizing group described in BIOS 1901, FIAT 943; 3-alkoxy-5-pyrazolone couplers as described in U.S. Pat. No. 2,439,098; 3-acylamino-5-pyrazolone couplers as described in U.S. Pat. Nos. 2,600,788; 3,062,653; etc.; 3-amino-5-pyrazolone couplers as described in British Pat.
  • Typical preferable magenta-forming couplers include the following couplers.
  • the nuclei for the couplers which can be used in the present invention providing cyan dyes compounds having a phenolic hydroxy group, in particular, phenolic compounds and ⁇ -naphtholic compounds, are useful.
  • phenol derivatives substituted with an acylamino group at the o- or m-position and ⁇ -naphthol derivatives substituted with a carbamyl group at the 2-position are particularly useful.
  • the ballasting group containing a hydrophobic residue is usefully introduced into the coupler nucleus as the acylamino group or as the carbamyl group.
  • the p-position to the hydroxy group is the reaction site with an oxidized aromatic primary amino color developing agent.
  • This reaction site can be either unsubstituted or substituted with a residue which can be eliminated by the oxidized developing agent.
  • Other nucleus positions can be substituted with a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, a sulfonamido group, a carbamyl group, a sulfamyl group, an alkoxycarbonyl group, a cyano group, a nitro group, a carboxy group, a sulfo group, a heterocyclic group (e.g., a 2-triazolyl group, a 2-imidazolyl group, etc.), and the like.
  • the phenolic hydroxy group can be converted into an acylated form which can be hydrolyzed by an alkaline aqueous solution.
  • the ballasted couplers which can be advantageously used in the present invention providing non-diffusible cyan dyes can be selected from those known and described in Mees and James, supra, and by Pelz, supra, or in other literature.
  • Typical preferred cyan-forming couplers include the following couplers.
  • couplers which can be used in the present invention providing diffusible dyes are reactive, non-diffusible, substantially colorless compounds which are capable of coupling with an oxidized developing agent and which, as a result of the coupling reaction, eliminate and release a dye soluble and diffusible in the developing composition.
  • Such couplers can be represented by the following general formula;
  • Cp represents a coupling reactive structure moiety in which the coupling position is substituted with the (Bl)-L-residue and, when the coupler is used in combination with a developing agent without a water-solubilizing group such as a sulfo group or a carboxy group, the Cp residue contains a water-solubilizing group (e.g., a sulfo group, a carboxy group, a sulfonamido group, etc.) in at least one non-coupling position.
  • a water-solubilizing group e.g., a sulfo group, a carboxy group, a sulfonamido group, etc.
  • the coupling reactive structure moiety utilized as Cp many functional groups which are known to undergo an oxidative coupling reaction with an aromatic primary amino color developing agent can be illustrated.
  • Suitable examples include phenols, anilines, cyclic or open-chain active methylene compounds, and hydrazones.
  • Particular examples of particularly useful reactive structure moieties include those derived from acylamino-substituted phenols, 1-hydroxy-2-naphthoic acid amides, N,N-dialkylanilines, 1-aryl-5-pyrazolones (the 3-position being substituted with an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, a ureido group or a sulfonamido group), pyrazolobenzimidazoles, pyrazolotriazoles, ⁇ -cyanoacetophenones and ⁇ -acylacetanilides.
  • the connecting or linkage group L whose bond to the coupler structure moiety is cleaved with an oxidized developing agent can be an azo group, an azoxy group, a mercuryl group (--HG--), an oxy group, a thio group, a dithio group, a triazolyl group, a diacylamino group, an acylsulfonamino group ##EQU7## an acyloxy group, a sulfonyloxy group, and an alkylidene group.
  • an oxy group, a thio group, a dithio group, a diacylamino group, an acyloxy group, etc. which are eliminated as an anion, are useful since a large amount of the diffusible dye is released.
  • the coupling position of the coupling structure moiety of the phenol or naphthol is preferably substituted with a group connected through an oxy group, a thio group or a diacyloxy group.
  • the coupling position of a pyrazolone is preferably substituted with an azo group, a thio group, or an acyloxy group
  • the coupling position of an acylacetanilide is preferably substituted with an oxy group, a thio group or a diacylamino group.
  • the hydrophobic residues contained in the residues represented by Bl are essentially same as the above-described hydrophobic groups of the couplers providing non-diffusible dyes, and impart a cohesive force between the coupler molecules in an aqueous medium to render the molecules non-diffusible in a hydrophilic colloid constituting a light-sensitive material.
  • a substituted or unsubstituted alkyl group, an alkenyl group, an aralkyl group and an alkylaryl group, having about 8 or more carbon atoms can be advantageously used.
  • Specific examples include a lauryl group, a stearyl group, an oleyl group, a 3-n-pentadecylphenyl group, a 2,4-di-t-amylphenoxy group, and the like.
  • hydrophobic residues can be connected, directly or through a divalent bond such as an amido bond, a ureido bond, an ether bond, an ester bond or a sulfonamido bond, to residues such as an aryl group or a heterocyclic group to form Bl.
  • the water-solubilizing group contained in the residue represented by Cp is an acidic group capable of being substantially dissociated in a processing composition or a precursor which provides such an acidic group upon hydrolysis.
  • acidic groups having a pKa of not more than about 11 are useful.
  • Examples of such groups are a sulfo group, a sulfuric ester group (--O--SO 3 H), a carboxy group, a sulfonamido group, a diacylamino group, a cyanosulfonamino group, a phenolic hydroxy group, etc.
  • the diffusible dye-releasing couplers which can be used in the present invention undergo, upon reaction with an oxidized developing agent, cleavage of the L--Cp bond to provide a soluble dye, which is an oxidative coupling reaction product between Cp and the developing agent, and a non-diffusible, substantially colorless, eliminated product derived from Bl--L--.
  • the resulting soluble dye diffuses into an image-receiving layer to form a dye image there.
  • Suitable diffusible dye-providing couplers which can be used in the present invention with advantage include the following couplers.
  • the aromatic primary amino developing agents which can be used in this invention advantageously include p-aminophenols, p-phenylenediamines and the derivatives thereof.
  • the ballasted couplers can be dispersed in a carrier, hydrophilic colloid, using various methods depending upon the type of the dye image-providing material.
  • couplers having a dissociative group such as a sulfo group or a carboxy group can be added to the hydrophilic colloid solution after being dissolved in water or in an alkaline aqueous solution.
  • couplers which are slightly soluble in an aqueous medium and readily soluble in an organic solvent the couplers are first dissolved in an organic solvent, and then the resulting solution is added to a hydrophilic colloid solution, followed by stirring or the like to disperse the solution as fine particles.
  • Suitable solvents are ethyl acetate, tetrahydrofuran, methyl ethyl ketone, cyclohexanone, ⁇ -butoxy- ⁇ -ethoxyethyl acetate, dimethylformamide, dimethylsulfoxide, 2-methoxyethanol, tri-n-butylphthalate, etc.
  • those solvents which possess a comparatively high vapor pressure can be evaporated upon drying of the photographic layers, or can be evaporated using the method described in U.S. Pat. Nos. 2,322,027 and 2,801,171 prior to coating.
  • those solvents which are readily soluble in water can be removed by washing with water according to the method described in U.S. Pat. Nos. 2,949,360 and 3,396,027.
  • Suitable high boiling solvents suitable for this purpose include fatty acid esters such as triglycerides of higher fatty acids and dioctyl adipate; phthalic esters such as di-n-butyl phthalate; phosphoric esters such as tri-o-cresyl phosphate and tri-n-hexyl phosphate; amides such as N,N-diethyllaurylamide; hydroxy compounds such as 2,4-di-n-amylphenol; and the like. Furthermore, in order to stabilize the dispersion of the coupler and to accelerate the step of dye image formation, it is advantageous to incorporate in the light-sensitive element a polymer having affinity for the solvent together with the coupler.
  • Polymers having affinity for the solvent and being suitable for this purpose include shellac, phenol-formaldehyde condensates, poly-n-butyl acrylate, n-butyl acrylate-acrylic acid copolymers, n-butyl acrylate-styrene-methacrylamide copolymers, and the like. These polymers can be dispersed in an organic solution together with the coupler and then dispersed in a hydrophilic colloid, or can be added, as a hydrosol prepared by emulsion polymerization or the like, to a hydrophilic colloid dispersion of the coupler.
  • the dispersion of the coupler can effectively be conducted under great shearing force.
  • a high speed rotary mixer, a colloid mill, a high pressure milk homogenizer, a high pressure homogenizer as described in British Pat. No. 1,304,264, an ultrasonic emulsifying apparatus, and the like are useful.
  • the use of a surface active agent as an emulsfying aid markedly serves to disperse the dye image-providing material.
  • Typical surface active agents useful for the dispersion of the dye image-providing material used in the present invention are sodium triisopropylnaphthalenesulfonate, sodium dinonylnaphthalenesulfonate, sodium p-dodecylbenzenesulfonate, sodium dioctyl sulfocussinate, sodium cetyl sulfate and the anionic surface active agents as described in Japanese Patent Publication No. 4293/64.
  • the combined use of these anionic surface active agents and higher fatty acid esters of anhydrohexitol shows particularly good emulsifying ability as described in U.S. Pat. No. 3,676,141.
  • the silver halide emulsion which can be used in the present invention is a colloidal dispersion of silver chloride, silver bromide, silver chlorobromide, silver bromoiodide, silver chlorobromoiodide or a mixture thereof.
  • the halide composition is selected depending upon the purpose of the end use of the light-sensitive material and the processing conditions. In particular, a silver bromoiodide emulsion or a silver chlorobromoiodide emulsion containing about 1 mol% to 10 mol% iodide, not more than about 30 mol% chloride and the balance bromide is desirable.
  • Useful silver halide grains have a mean grain size of about 0.1 ⁇ to about 2 ⁇ .
  • silver halides having a uniform grain size are preferred.
  • the grains can be in a cubic form, an octahedral form or in a mixed crystal form.
  • These silver halide emulsions can be prepared using known conventional processes as described in P. Galfkides, Chimie Photographique, 2nd Ed., Chapters 18 to 23, Paul Montel, Paris (1957). That is, a soluble silver salt such as silver nitrate and a water-soluble halide such as potassium bromide are reacted with each other in the presence of a solution of protective colloid such as gelatin and crystals are allowed to develop in the presence of excess silver halide or a solvent for silver halide such as ammonia.
  • a single or double jet method or a pAg-controlled double jet method can be employed as the precipitating method.
  • Removal of the soluble salts from the emulsion can be effected by washing and dialysis of the cool-set emulsion, by the combination of the addition of a sedimenting agent such as an anionic polymer having sulfone groups, sulfuric ester groups or carboxy groups or an anionic surface active agent and the adjustment of pH, or by the combination of the use of an acylated protein such as phthaloyl gelatin as a protective colloid and the adjustment of pH, to thereby cause sedimentation.
  • a sedimenting agent such as an anionic polymer having sulfone groups, sulfuric ester groups or carboxy groups or an anionic surface active agent and the adjustment of pH
  • an acylated protein such as phthaloyl gelatin as a protective colloid
  • the silver halide emulsions used in the present invention are preferably subjected to chemical sensitization employing a heat-treatment using the natural sensitizers contained in gelatin, a sulfur sensitizer such as sodium thiosulfate or N,N,N'-trimethylthiourea, a gold sensitizer such as a thiocyanate complex salt or thiosulfate complex salt of monovalent gold, or a reducing sensitizer such as stannous chloride or hexamethylene tetraamine.
  • emulsions which tend to form latent images on the surface of the silver halide grains and emulsions which tend to form latent images inside the silver halide grains as described in U.S. Pat. Nos. 2,592,550; 3,206,313, etc. can be used in the present invention.
  • the silver halide emulsions which can be used in the present invention can be stabilized with additives such as 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 5-nitroimidazole, 1-phenyl-5-mercaptotetrazole, 8-chloromercuriquinoline, benzenesulfinic acid, pyrocatechin, etc.
  • additives such as 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene, 5-nitroimidazole, 1-phenyl-5-mercaptotetrazole, 8-chloromercuriquinoline, benzenesulfinic acid, pyrocatechin, etc.
  • inorganic compounds such as cadmium salts, mercury salts, complex salts of platinum group metals such as the chloro complex salt of palladium, and the like are also useful for stabilizing the light-sensitive material of the present invention.
  • the silver halide emulsions which can be used in the present invention can
  • the silver halide emulsions used in the present invention can possess, if desired, a color sensitivity expanded with optical sensitizing dyes.
  • optical sensitizing dyes are cyanines, merocyanines, holopolar, cyanines, styryls, hemicyanines, oxanols, hemioxanols, and the like. Specific examples of optical sensitizing agents are described in P. Glafkides, supra, Chapters 35 to 41, and F. M. Hamer, The Cyanine Dyes and Related Compounds, (Interscience).
  • cyanines in which a nuclear nitrogen atom is substituted with an aliphatic group having a hydroxy group, a carboxy group or a sulfo group are especially useful for the practice of the present invention.
  • the processing composition permeable layers used in the present invention such as the silver halide emulsion layer, the dye image-providing material-containing layer and the auxiliary layers (e.g., a protective layer, an interlayer, etc.) contain a hydrophilic polymer as a binder.
  • Suitable hydrophilic polymers are gelatin, casein, gelatin modified with an acylating agent or the like, vinyl polymer-grafted gelatin, proteins such as albumin, cellulose derivatives such as hydroxyethyl cellulose, methyl cellulose, carboxymethyl cellulose, etc., polyvinyl alcohol, a partially hydrolyzed product of polyvinyl acetate, polyvinyl pyrrolidone, high molecular weight non-electrolytes such as polyacrylamide, polyacrylic acid, a partially hydrolyzed product of polyacrylamide, anionic synthetic polymers such as vinyl methyl ether-maleic acid copolymers, N-vinylimidazole-acrylic acid-acrylamide copolymers, synthetic polymer amphoteric electrolytes such as polyacrylamide having been subjected to the Hofmann reaction.
  • hydrophilic polymers can be used alone or in combination.
  • these hydrophilic polymer layers can contain a latex-like polymer dispersion or hydrophobic monomers such as an alkyl acrylate, an alkyl methacrylate, etc.
  • These polymers, particularly polymers having functional groups such as an amino group, a hydroxy group or a carboxy group can be rendered insoluble with various cross-linking agents without loss of processing solution composition permeability.
  • Particularly useful cross linking agents include aldehyde compounds such as formaldehyde, glyoxal, glutaraldehyde, mucochloric acid, acrolein oligomer, etc.; aziridine compounds such as triethylenephosphoramide as described in Japanese Patent Publication No.
  • hydrophilic polymers can contain a cross linking-accelerating agent such as a carbonate or resorcin as well as the cross linking agent.
  • the photographic layers used in the present invention can be coated using various coating methods such as a dip coating method, a roller coating method, an air knife coating method, a bead coating method as described in U.S. Pat. No. 2,681,294, a curtain coating method as described in U.S. Pat. Nos. 3,508,947 and 3,513,017.
  • a dip coating method a roller coating method
  • an air knife coating method a bead coating method as described in U.S. Pat. No. 2,681,294
  • a curtain coating method as described in U.S. Pat. Nos. 3,508,947 and 3,513,017.
  • the coating composition advantageously can contain a variety of surface active agents as coating aids.
  • Useful coating aids include nonionic surface active agents such as saponin, p-nonylphenol-ethyleneoxide adducts, alkyl ethers of sucrose, glycerin monoalkyl ethers, etc., anionic surface active agents such as sodium dodecylsulfate, sodium p-dodecylbenzenesulfonate, sodium dioctylsulfosuccinate, etc.; and amphoteric surface active agents such as carboxymethyl-dimethyllauryl ammonium hydroxide inner salt, "Deriphat 151,” trade name produced by General Mills, Inc., betaine compounds as described in U.S. Pat. No. 3,441,413, British Pat. No. 1,159,825 and Japanese Patent Publication No. 21985/71.
  • the coating composition can contain various thickening agents.
  • thickening agents for example, in addition to those which increase the viscosity of the coating composition due to their own viscosity such as high molecular weight polyacrylamide, anionic polymers such as cellulose sulfate, poly-p-sulfostyrene potassium salt and acrylic polymers as described in U.S. Pat. No. 3,655,407 which exhibit a thickening action due to mutual interaction with a binder polymer contained in the coating composition are similarly useful.
  • the processing composition which can be used in the present invention is a liquid composition containing the processing components necessary for the development of the silver halide emulsion and necessary for the formation of the diffusion transfer dye image.
  • the main solvent therein is water and, in some cases, a hydrophilic solvent such as methanol or methyl Cellosolve is additionally present.
  • the processing composition contains alkali in an amount sufficient to maintain the pH at a level necessary for causing development of the emulsion layer and neutralizing acids produced during the various steps of development and dye image formation.
  • Typical alkalis are sodium hydroxide, potassium hydroxide, calcium hydroxide dispersion, tetramethylammonium hydroxide, sodium carbonate, trisodium phosphate, diethylamine, etc.
  • the processing composition preferably possesses a pH of not less than about 12 at room temperature (about 20° ⁇ 30°C). More preferably, the processing composition contains a hydrophilic polymer such as a high molecular weight polyvinyl alcohol, hydroxyethyl cellulose, sodium carboxymethyl cellulose or the like. These polymers impart to the processing composition a viscosity of not less than about 1 poise, preferably about 1,000 poise, at room temperature, which not only facilitates the uniform spreading of the composition upon processing but also the formation of an immovable film, upon concentration of the processing solution due to migration of the aqueous solvnet into the light-sensitive element and the image-receiving element in the course of the processing, thus serving to unify the film unit after processing.
  • this polymer film can serve, after the substantial completion of the formation of the diffusion transfer dye image, to control further migration of coloring ingredients into the image-receiving layer, thereby preventing the image from being changed.
  • the processing composition advantageously contains a light absorbent such as carbon black and a desensitizer as described in U.S. Pat. No. 3,579,333 so as to prevent the silver halide emulsion from being fogged by ambient light during processing.
  • the processing composition advantageously contains additives such as a developer (e.g., a primary amino color developing agent, etc.), an antioxidizing agent (e.g., a sulfite, ascorbic acid, etc.), an antifogging agent (e.g., a halogen compound, 5-nitrobenzimidazole, etc.), and the like.
  • Suitable examples of silver halide solvents contained in the processing composition include alkali metal thiosulfates such as sodium thiosulfate and potassium thiosulfate, ammonium thiosulfate and alkyl (CH 3 or C 2 H 5 ) bissulfonylmethane, etc.
  • Alkali metal thiocyanates such as sodium and potassium thiocyanates, ammonium thiocyanate and uracil can be used in combination with the above compounds.
  • a suitable amount is about 4 g/l to 9 g/l in the processing composition.
  • the processing composition used in the present invention is advantageously retained in a rupturable container.
  • a container is advantageously produced by folding a sheet of a liquid- and air-impervious substance and sealing each edge to form a cavity in which the processing composition is retained, and the container is advantageously formed so that, when the film unit passes through pressure-applying members, the container is ruptured at a given portion due to the inner hydraulic pressure generated within the processing composition to thereby release the contents.
  • Suitable advantageous materials for forming the container are a polyethylene terephthalate/polyvinyl alcohol/polyethylene laminate, a lead foil/vinyl chloride-vinyl acetate copolymer laminate or the like.
  • This container is desirably fixedly positioned and extends transverse a leading (i.e., in the direction of travel of the film unit with respect to the pressure applying members) edge of the film unit whereby to effect a substantially unidirectional discharge of the contents of the container on the surface of the light-sensitive element.
  • Preferred examples of such containers are described in U.S. Pat. Nos. 2,543,181; 2,643,886; 2,653,732; 2,723,051; 3,056,491; 3,056,492; 3,152,515 and 3,173,580. These containers are advantageous for the practice of the present invention.
  • the image-receiving element used in the invention fixes the dye image-forming materials such as the diffusible dyes, etc., which are released with an imagewise distribution from dye image-providing materials associated with the silver halide emulsion.
  • the image-receiving element preferably contains a basic polymer or a basic surface active agent.
  • the basic polymer those polymers which contain tertiary or quaternary nitrogen atoms are excellent.
  • More specifically illustrative examples are poly-4-vinylpyridine, a polymer of the aminoguanidine derivative of vinyl methyl ketone as described in U.S. Pat. No. 2,882,156, poly-4-vinyl-N-benzyl-pyridinium p-toluenesulfonate, poly-3-vinyl-4-methyl-N-n-butyl-pyridinium bromide, styrene/N-(3-maleimidopropyl)-N,N-dimethyl-N-4-phenylbenzyl-ammonium chloride copolymer as described in British Pat. No.
  • suitable examples are N-laurylpyridinium bromide, cetyltrimethylammonium bromide, methyl-tri-n-laurylammonium p-toluenesulfonate, methyl-ethyl-cetylsulfonium iodide, benzyltriphenylphosphonium chloride, etc.
  • multi-valent metals such as thorium, aluminum, zirconium, etc., also exert a fixing action on the anionic dye image-forming materials.
  • These substances advantageously form films together with polymers such as gelatin (in particular acid-processed gelatin), polyvinyl alcohol, polyacrylamide, polyvinyl methyl ether, hydroxyethyl cellulose, N-methoxymethylpolyhexylmethyleneadipamide, polyvinylpyrrolidone, etc.
  • polymers such as gelatin (in particular acid-processed gelatin), polyvinyl alcohol, polyacrylamide, polyvinyl methyl ether, hydroxyethyl cellulose, N-methoxymethylpolyhexylmethyleneadipamide, polyvinylpyrrolidone, etc.
  • the dye image-forming material is one component for forming a dye such as a diffusible coupler
  • the image-receiving layer contains other coupling components capable of reacting with this component to form a dye, such as a p-phenylenediamine derivative and an oxidizing agent, or a diazonium compound.
  • This type of image-receiving element which can be used is described in U.S. Pat. Nos. 2,647,049; 2,661,293; 2,698,244; 2,698,798; 2,802,735; 3,676,124, British Pat. Nos. 1,158,440; 1,157,507, etc.
  • the film unit of the present invention can contain a developing agent scavenger which reacts with excess developing agent remaining after the processing to form a colorless product which is difficult to oxidize.
  • a film unit which contains the above-described scavenger in the acidic substance-containing neutralizing layer, in the timing layer or in the image-receiving layer of the film unit provides distinct images with less stain.
  • Film units which contain an aromatic primary amino developing agent, which tends to cause stain advantageously contain as the scavenger a compound having a functional group capable of condensing with amines, such as an isocyanate, an aldehyde precursor and a vinylsulfonyl compound as described in German Pat. OLS Nos. 2,201,392; 2,225,480 and 2,225,497.
  • the diffusion transfer photographic film unit used in the present invention preferably possesses the function of neutralizing the alkali brought thereinto from a processing composition.
  • the processing composition contains alkali so as to provide a pH of higher than about 10, preferably higher than 11, which is sufficiently high to accelerate the image-forming steps comprising the development of the silver halide emulsion, the formation of the diffusible dye image-forming material and the diffusion transfer.
  • the pH in the film unit is reduced to around neutrality, i.e., less than about 9, preferably less than 8, whereby further image-formation is actually discontinued to prevent the image tone from being changed with the lapse of time and to control discoloration and fading of the images and stain of white background due to high alkalinity.
  • the film unit advantageously contains a neutralizing layer containing an acidic substance in a sufficient quantity to neutralize the alkali contained in the processing composition to the above-described pH, that is, in an area concentration equivalent to or greater than the amount of alkali contained in the spread processing composition.
  • Preferred acidic substances are those which contain an acidic group having a pKa of less than about 9, particularly a carboxy group or a sulfonic acid group, or which contain a precursor group capable of providing such an acidic group upon hydrolysis. More preferred examples are higher fatty acids such as oleic acid as described in U.S. Pat. No.
  • 2,983,606 polymers of acrylic acid, methacrylic acid or maleic acid, the partially esterified polymers thereof, or acid anhydrides.
  • high molecular weight acidic substances are copolymers of a vinyl monomer (e.g., ethylene, vinyl acetate, vinyl methyl ether, etc.) and maleic anhydride, and the n-butyl half ester thereof; copolymers of butyl acrylate and acrylic acid; cellulose acetate, hydrogen phthalate; and the like.
  • the neutralizing layer can contain polymers such as cellulose nitrate and polyvinyl acetate, and a plasticizer as described in U.S. Pat. No. 3,557,237.
  • the neutralizing layer can be hardened through cross linking with a multifunctional aziridine compound, an epoxy compound, etc.
  • the neutralizing layer can be positioned in either the image-receiving element and/or the light-sensitive element.
  • the neutralizing layer is advantageously positioned between the support of the image-receiving element and the image-receiving layer.
  • the acidic substances can be microencapsulated for incorporation in the film unit.
  • the neutralizing layer or the acidic substance-containing layer used in the present invention is desirably separated from the spread processing composition layer by a neutralization rate-controlling layer or timing layer.
  • This timing layer functions to prevent a disadvantageous reduction in the transfer image density due to a too fast reduction in pH before the necessary development of the silver halide emulsion layer and the formation of the diffusion transfer image are completed. That is, this layer functions to delay the reduction in the pH until the necessary development and transfer are completed.
  • the image-receiving element possesses a multi-layered structure comprising a support--a neutralizing layer--a timing layer-- a mordant layer (image-receiving layer) in this sequence.
  • the timing layer comprises mainly polymers such as gelatin, polyvinyl alcohol, polyvinyl propyl ether, polyacrylamide, hydroxypropylmethyl cellulose, isopropyl cellulose, copolymer of polyvinyl alcohol and polyvinyl butyral, partially hydrolyzed polyvinyl acetate, copolymers of ⁇ -hydroxyethyl methacrylate and ethyl acrylate, and the like. These polymers are usefully hardened through cross linking with an aldehyde compound such as formaldehyde, or an N-methylol compound.
  • the timing layer preferably has a thickness of about 2 ⁇ to 20 ⁇ .
  • a blue-sensitive silver halide emulsion, a green-sensitive silver haldie emulsion and a red-sensitive silver halide emulsion are positioned in sequence from the side to be exposed.
  • a yellow filter can be positioned between the blue-sensitive silver halide emulsion and the green-sensitive silver halide emulsion.
  • This yellow filter layer contains a yellow colloidal silver dispersion, an oil-soluble yellow dye dispersion, an acidic dye mordanted with a basic polymer, or a basic dye mordanted with an acidic polymer.
  • the emulsion layers are advantageously separated from each other by interlayers.
  • the interlayers prevent disadvantageous mutual interactions from occurring between the emulsion layer units having different color sensitivities.
  • the interlayer is formed by a porous polymer containing fine pores and comprises a latex of a hydrophilic polymer and hydrophobic polymer, as described in U.S. Pat. No. 3,625,685 or a polymer whose hydrophilicity is gradually increased by the processing composition, such as calcium alginate, as described in U.S. Pat. No. 3,384,483, as well as a hydrophilic polymer such as gelatin, polyacrylamide, a partially hydrolyzed product of polyvinyl acetate, etc.
  • the interlayer is effective for a reducing agent such as a ballasted hydroquinone derivative and a ballasted coupler capable of being fixed by the reaction with the oxidation product, to prevent the oxidation product of a developing agent from exchanging between emulsion units. Furthermore, in order to attain good color reproduction, in a system wherein image reversion is effected by dissolution-physical development, it is effective to further incorporate in the interlayer physical development nuclei such as colloidal metallic silver in the interlayer.
  • a reducing agent such as a ballasted hydroquinone derivative and a ballasted coupler capable of being fixed by the reaction with the oxidation product
  • the support which can be used in the present invention is a substantially planar substance which does not undergo any serious dimensional change due to the processing composition used during processing.
  • rigid supports such as a glass plate can be used.
  • flexible supports are useful. Suitable flexible supports which can be advantageously used are those generally used for photographic light-sensitive materials, such as a cellulose nitrate film, a cellulose acetate film, a polyvinyl acetal film, a polystyrene film, a polyethylene terephthalate film, a polycarbonate film, etc.
  • Supports having dimensional stability and oxygen impervious properties such as a laminate in which a polyvinyl alcohol layer is sandwiched between polyethylene terephthalate layers or between cellulose acetate layers is particularly desirable since the laminate serves to provide a stable dye image and is stained to a lesser extent.
  • an aqueous vapor permeable support such as is described in U.S. Pat. No. 3,573,044.
  • the transparent support is desirably colored to such extent that transmission of light in a planar direction to the support can be prevented without inhibiting imagewise exposure and observation therethrough.
  • the support can contain a plasticizing agent such as a phosphoric ester, a phthalic ester, etc., an ultraviolet light-absorbing agent such as 2-(2-hydroxy-4-t-butylphenyl)-benzotriazole, etc., an antioxidant such as a hindered phenol, etc.
  • the support In order to maintain the adhesion between the support and the hydrophilic polymer-containing layer, it is advantageous to provide a subbing layer or to subject the surface of the support to a preliminary treatment such as corona discharge, irradiation with ultraviolet light or a flame treatment.
  • the support usually has a thickness of about 20 to 300 ⁇ .
  • a light-reflective substance is positioned between the image-receiving layer and the light-sensitive unit surface by the time of completion of the processing at the latest in order to form a white background of the dye image formed in the image-receiving layer.
  • Suitable light-reflecting substances are titanium dioxide, barium sulfate, zinc oxide, alumina, barium stearate, calcium carbonate, silicon dioxide, zirconium oxide, kaolin, magnesium oxide, etc. These substances can be used alone or in combination.
  • Such light-reflecting substance can be either initially formed or, as is described in U.S. Pat. Nos.
  • the light-reflecting substance can be incorporated in the layer which contains as a binder a hydrophilic polymer such as polyvinyl alcohol, gelatin, hydroxypropyl cellulose, polyvinyl pyrrolidone, etc. Furthermore, the light-reflecting substance can be compounded in the processing composition so that, upon spreading of the processing composition, the substance is fixed in a dispersed state in a layer of a film-forming polymer such as hydroxyethyl cellulose or carboxymethyl cellulose formed upon spreading the processing composition.
  • a hydrophilic polymer such as polyvinyl alcohol, gelatin, hydroxypropyl cellulose, polyvinyl pyrrolidone, etc.
  • the light-reflecting substance can be compounded in the processing composition so that, upon spreading of the processing composition, the substance is fixed in a dispersed state in a layer of a film-forming polymer such as hydroxyethyl cellulose or carboxymethyl cellulose formed upon spreading the processing composition.
  • a light-reflecting substance and a fluorescent brightening agent such as a stilbene, a coumarin, triazine, an oxazole, etc.
  • a fluorescent brightening agent such as a stilbene, a coumarin, triazine, an oxazole, etc.
  • a dye which is colored at a pH higher than the pKa of the dye and which becomes colorless at a pH less than the pKa is advantageous to incorporate, as is described in U.S. Pat. Nos. 3,647,437 and 3,702,245, a dye which is colored at a pH higher than the pKa of the dye and which becomes colorless at a pH less than the pKa.
  • the light-reflecting substance-containing layer advantageously has a light-reflecting substance/binder polymer composition ratio (by weight) of about 0.5 to about 100, and has a dry thickness of about 5 ⁇ to 50 ⁇ . Also, the light-reflecting substance-containing layer possesses a reflectivity of not less than about 50%, preferably not less than 70%.
  • the film unit of the present invention has a rupturable container retaining the processing composition. When pressed by pressure-applying members, this container is ruptured due to the internal pressure to release the processing composition in a predetermined manner.
  • pressure-applying members can be used.
  • a pressure-applying member which comprises at least one pair of members juxtaposed with a certain gap or clearance is suited for the processing of the film unit of the present invention.
  • a pair of members are fixedly positioned with a certain clearance or oppose one another through a spring or a like elastic body.
  • the members can be rod-shaped, freely rotary rollers or motor-driven rollers.
  • development processing is continued outside a camera, e.g., in a bright place.
  • the silver halide emulsion layers are protected from ambient light until the development and the transfer of dye images are substantially completed.
  • a light-intercepting layer containing a light absorbent on the silver halide emulsion side.
  • This light-intercepting layer is constituted so as to be processing composition permeable (hydrophilic) or processing composition impermeable (dimensionally stable), depending upon the position of the layer.
  • the processing composition-permeable light-intercepting layer is a water permeable polymer layer of gelatin, polyvinyl alcohol, polyacrylamide, polyhydroxyethyl cellulose, carboxymethyl cellulose sodium salt, methyl cellulose, etc., containing a light-intercepting substance.
  • This layer can be either coated in advance as a pre-formed layer or can be spread upon processing as a processing composition layer.
  • the light-intercepting layer with dimensional stability is a polymer layer containing a light absorbent, as is described in Japanese Patent Publication No. 24547/68 and U.S. Pat. No. 3,607,818. This is contained in a film unit as a support or a light-intercepting element.
  • this dimensionally stable light-intercepting layer can be prepared from a foil or a metal such as aluminum, tin, etc., a laminate film of a metal foil and a polymer or a polyethylene terephthalate film having vacuum deposited thereon aluminum and a laminate film. It is preferred, from the standpoint of increased light-intercepting property and of beautiful appearance, to cover the light-intercepting layer with a light-reflecting substance such as titanium dioxide. Various light absorbents can be used in the light-intercepting layer.
  • carbon powder such as carbon black, colloidal silver, organic pigments such as azo lake or copper phthalocyanine, water-insoluble azo dyes, an anthraquinone dye dispersion, polymers having been reacted with a reactive dye and micelle-forming hydrophilic dyes are useful.
  • the light-intercepting layer it is necessary for the light-intercepting layer to possess an absorbance (to diffused light) of not less than about 3, preferably not less than 5 over the entire wavelength region of from about 350 m ⁇ to 650 m ⁇ , preferably, from about 300 m ⁇ to 750 m ⁇ , although this depends upon the purpose of use of the film unit.
  • the dimensionally stable light-intercepting layer can advantageously be used as an adhesive tape in order to cover the edges of the transparent support thereby preventing light leakage through the edges of the film unit to the silver halide emulsion layers.
  • FIG. 1 illustrates a cross sectional view of specific examples of the light-sensitive element, the image-receiving element and the processing composition container.
  • the accompanying figure is drawn to clearly show the disposition of each constituent. Dimensions are not proportional and, in some cases, are greatly exaggerated.
  • Light-sensitive element 1 contains light-sensitive member 61 which comprises transparent support 51 having provided on the one side of transparent support 51, in sequence, diffusible yellow dye-releasing light-insensitive layer 52, blue-sensitive silver halide emulsion layer 53 providing a non-diffusible yellow dye image, yellow filter layer 54, diffusible magenta dye-releasing light-insensitive layer 55, green-sensitive silver halide emulsion layer 56 providing a non-diffusible magenta dye image, interlayer 57, diffusible cyan dye-releasing light-insensitive layer 58 and red-sensitive silver halide emulsion layer 59 providing a non-diffusible cyan dye image.
  • light-sensitive member 61 which comprises transparent support 51 having provided on the one side of transparent support 51, in sequence, diffusible yellow dye-releasing light-insensitive layer 52, blue-sensitive silver halide emulsion layer 53 providing a non-diffusible yellow dye image, yellow filter layer 54, diffusible magenta dye-releasing light-insensitive
  • Image-receiving element 2 contains image-receiving member 74 which comprises transparent support 70 having provided thereon, in sequence, neutralizing layer 71 containing an acidic substance, timing layer 72 and image-receiving layer 73.
  • Processing solution container 4 is a pod prepared from, e.g., a laminate film of lead foil 92 and alkali-resistant polymer layer 91, and retains processing solution 93. Upon application of pressure to the processing solution container, the container is ruptured due to the inner pressure of the processing composition to release the contents.
  • FIG. 2 shows one embodiment of the film unit of the present invention.
  • FIG. 2a shows the appearance of the light-sensitive side
  • FIG. 2b the appearance of the transferred image side.
  • numeral 1 designates a light-sensitive element
  • 2 an image-receiving element
  • 3 a light-intercepting element
  • 4 a processing composition container
  • 8 a white bordering sheet of the transferred image
  • 9 a coating layer for covering the edges to intercept light.
  • light-sensitive element 1 is supported in a camera by pressure plate 100 and is connected to leader paper 5 at the leading edge in the direction of travel.
  • Image-receiving element 2 and light-intercepting element 3 are connected, respectively, to leader paper 6 and 7 each at the leading edge.
  • These leader papers 5, 6 and 7 are connected to each other.
  • the three elements are disposed so that they can be superposed one over the other with all edges meeting, by drawing the tip of leader paper 5.
  • Processing solution container 4 is disposed on a leader paper so that the contents can be released between the light-sensitive element and the image-receiving element.
  • FIG. 4 shows a cross sectional view of the film unit illustrated in FIG 3.
  • FIG. 4 shows that the light-sensitive element is disposed so as to be superposed with both backing layer 50 and transparent support 51 directed outside and both light-sensitive member 61 and light-intercepting layer 60 inside, and that the image-receiving element is disposed so as to be superposed with transparent support 70 directed outside and image-receiving member 74 inside.
  • FIG. 4 shows that the light-sensitive element is disposed so as to be superposed with both backing layer 50 and transparent support 51 directed outside and both light-sensitive member 61 and light-intercepting layer 60 inside, and that the image-receiving element is disposed so as to be superposed with transparent support 70 directed outside and image-receiving member 74 inside.
  • FIG. 4 also shows that the light-intercepting element is disposed so as to be superposed so that it can cover the backing layer and the transparent support of the light-sensitive element.
  • FIG. 4 further shows that the processing composition container is disposed so that the contents can be positioned between leader paper 5 associated with the light-sensitive element and leader paper 6 associated with the image-receiving element.
  • a laminate film comprising a 25 ⁇ -thick polyvinyl alcohol film having coated on both sides thereof 38 ⁇ -thick triacetylcellulose films were coated, in sequence, the following layers to prepare a light-sensitive element.
  • a diffusible yellow dye-providing layer containing 1.6 ⁇ 10.sup. -5 mol/100 cm 2 of diffusible yellow dye-providing coupler, ⁇ -pivaloyl- ⁇ -(3-octadecylcarbamylphenoxy)-3,5-dicarboxyacetanilide, 1 mg/100 cm 2 of t-octyhydroquinone, 12 mg/100 cm 2 of N,N-diethyllauramide, 0.1 mg/100 cm 2 of Carey-Lea type gold colloid and 16 mg/100 cm 2 of gelatin, the gold colloid being prepared by reducing chloroauric acid with sodium borohydride in the presence of gelatin and appearing pink.
  • a second diffusible yellow dye-providing layer containing 0.8 ⁇ 10 - 5 mol/100 cm 2 of diffusible yellow-providing coupler, ⁇ -pivaloyl- ⁇ -(3-octadecylcarbamylphenoxy)-3,5-dicarboxyactetanilide, 0.6 mg/100 cm 2 of t-octylhydroquinone, 6 mg/100 cm 2 of N,N-diethyllauramide, 0.05 mg/100 cm 2 of Carey-Lea type silver colloid and 8 mg/100 cm 2 of gelatin, the silver colloid being prepared by reducing silver nitrate with sodium borohydride in the presence of gelatin and appearing yellow.
  • SPC1 silver bromoiodide emulsion grains
  • SPC2 silver bromoiodide emulsion grains
  • a mixture comprising 50 g of carbon black (furnace type), 2.5 g of ⁇ -(4-octadecyloxybenzoyl)-2-methoxy-5-sulfoacetanilide potassium salt, 0.5 g of sodium hydroxide and 150 ml of water was kneaded using a colloid mill to prepare a paste. To this was added 500 g of a 10% aqueous solution of gelatin and, under stirring, a 5% citric acid solution was added thereto to adjust the pH to 5.5. Then, the resulting mixture was coated in a dry thickness of 4.5 ⁇ to complete a light-sensitive element.
  • a neutralizing transparent layer containing 300 mg/100 cm 2 of the half ester prepared by treating vinyl methyl ether-maleic anhydride copolymer with n-butyl alcohol, 60 mg/100 cm 2 of 1,4-bis(2',3'-epoxy)butane and 21 mg/100 cm 2 of hexahydro-1,3,5-triacryl-s-triazine.
  • a timing layer comprising 45 mg/100 cm 2 of n-butyl acrylate- ⁇ -hydroxyethyl methacrylate copolymer (monomer molar ratio: about 1.1).
  • the resulting surface was processed with a 1% acetone solution of polyethyleneglycol(1000)monocetyl ether to form a coating film of a thickness of about 0.5 ⁇ .
  • processing solutions having the following formulations containing as a development accelerator each of the following compounds were prepared.
  • a rupturable container capable of retaining 1 ml of each processing solution was prepared. The container was made by folding a laminate film of polyethylene-aluminum-cellophane-polyethylene and heat-sealing so that a cavity for retaining the processing solution was formed.
  • the processing composition was prepared and put into the container in the atmosphere of Freon gas (Freon 12).
  • the thus prepared light-sensitive element and the image-receiving element were cut into 10 ⁇ 8 cm size and the thus cut sheets were pressed to intimately adhere each other with the coated films facing each other.
  • a 115 ⁇ -thick, porous polyethylene terephthalate sheet containing titanium dioxide was adhered along the periphery of the image-receiving element so that it bordered the image.
  • the aforesaid processing solution-retaining container was fixedly positioned at the leading end of the resulting composite so that the contents could be released between the light-sensitive element and the image-receiving element.
  • a polyethylene terephthalate light-intercepting element of sufficient size to cover the light-sensitive surface and of a thickness of about 50 ⁇ containing 5% by weight carbon black was adhered along the leading end of the light-sensitive element, and an ethyl acetate solution of polyvinyl acetate containing carbon black was coated at the margins of the film composite to prevent light leakage through the edges.
  • film units as illustrated in FIGS. 2a and 2b containing the compound of the present invention in different amounts were completed.
  • Sensitometry was conducted by step-wise exposure of the film units through the transparent support of the light-sensitive element with the light-intercepting element moved out of the path of the light of exposure. After superposing the light-intercepting element, the film unit was passed through a pair of juxtaposed rollers to spread the processing composition in a thickness of 200 ⁇ . The processing was continued leaving each of the 8 film units in a bright room at 25°C. The formation of the transferred dye images was observed through the support of the image-receiving layer. The reflection density of the transferred images was measured using red(R), blue(B) and green(G) filters. The results thus obtained are shown in Table 1.
  • Film units were prepared in the same manner as in Example 1 except for using 1.8 ⁇ 10 - 5 mol/100 cm 2 of cyan-forming coupler, 1-hydroxy-N-[ ⁇ -(2,4-di-t-amylphenoxy)propyl]-2-naphthamide in place of the yellow-forming coupler in the third layer and in place of the magenta-forming coupler in the ninth layer contained in the light-sensitive unit.
  • 0.1 g of each of the following compounds of the present invention was added to the processing solution, and exposure, development, processing and sensitometry were conducted in the same manner as in Example 1. The results thus obtained are shown in Table 2.
  • Film units comprising the light-sensitive unit and the image-receiving unit described in Example 2 and the processing solution described in Example 1 containing 0.7 ml of aminoethylethanolamine as the compound of the present invention and film units not containing the compound of the present invention were prepared and subjected to similar exposure and development processing in Example 1.
  • the reflection density of the color images transferred to the image-receiving element was measured at definite intervals of time to examine the progress of the development. The results thus obtained are shown in Table 3.
  • film units to which the compound of the present invention had been added rapidly provided distinct images having a high contrast ( ⁇ D) and a high density (Dmax) of color images fixed in the image-receiving layer in a definite processing time, as compared with the film units to which the compound of the present invention had not been added.
  • Light-sensitive element and image-receiving elements were prepared in the same manner as in Example 1.
  • Six processing solutions were prepared by adding to the formulation shown in Example 1 the compound of the present invention, 2-hydroxy-1,3-diaminopropane, in an amount of 0, 0.01, 0.05, 0.2 or 1 ml.
  • 1.5 ml of each processing solution was placed in a rupturable container and the rupturable container then positioned between the light-sensitive element and the image-receiving element. Then, each of the resulting film units was exposed and processed to spread the processing solution in the same manner as in Example 1.
  • Sensitometry was conducted 10 minutes after the processing. The results thus obtained are shown in Table 4. Also, with the sample to which the compound of the present invention had been added in an amount of 0.2 ml, sensitometry was conducted after developing for 2,5 and 10 minutes to show the state of the progress of development.
  • the sensitizers of the present invention were compared with conventionally known sensitizers. As samples for testing, the following were used.
  • Light-sensitive Element A light-sensitive unit comprising a blue-sensitive negative-type silver halide emulsion layer (iodide content: 3.0 mol%; mean grain size: 0.8 ⁇ ) formed by multi-layer-coating the first layer through the fifth layer described in Example 1, an interlayer and a positive layer containing a gold colloid and a coupler capable of releasing a diffusable yellow dye.
  • Processing Solution Prepared in the same manner as in Example 1 except for changing the kind and the amount of the sensitizer to the following conventionally known sensitizers and the compound of the present invention as follows.
  • Image-receiving Layer same as in Example 1.
  • Example 6 The thus prepared samples were used and subjected to the same sensitometry as in Example 1.
  • the reflection density of the yellow dye transferred onto image-receiving sheet was measured through a blue filter. The results thus obtained are shown in Table 6.

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Silver Salt Photography Or Processing Solution Therefor (AREA)
US05/525,431 1973-11-20 1974-11-20 Diffusion transfer color film unit with hydroxy substituted alkylene amino development accelerators Expired - Lifetime US3960569A (en)

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US4053312A (en) * 1974-09-04 1977-10-11 Eastman Kodak Company O-sulfonamidonaphthol diffusible dye image providing compounds
US4186004A (en) * 1976-10-15 1980-01-29 Eastman Kodak Company Process of formation of color images, photographic product and treatment solutions useful therein
US4252894A (en) * 1975-10-22 1981-02-24 Gaf Corporation Hydrophilic color coupler composition containing diepoxide
US4273863A (en) * 1977-09-29 1981-06-16 Eastman Kodak Company Process of formation of color images, photographic product and treating solutions useful for putting the process into practice
US4511643A (en) * 1982-09-22 1985-04-16 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic element
US4547452A (en) * 1982-09-29 1985-10-15 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic element with sufinic acid
US4968588A (en) * 1986-01-30 1990-11-06 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials with a color developer comprising no benzyl alcohol and an accelerator

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JPS5131232A (en) * 1974-09-11 1976-03-17 Fuji Photo Film Co Ltd Kairyosareta chuwasoomotsushashinzairyo
JPS5574541A (en) * 1978-11-29 1980-06-05 Konishiroku Photo Ind Co Ltd Film unit for color diffusion transfer photography

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GB904364A (en) 1956-03-07 1962-08-29 Kodak Ltd Improvements in photographic processes
US3128183A (en) * 1960-06-17 1964-04-07 Eastman Kodak Co Photographic halide emulsions sensitized with alkylene oxide polymers and aliphatic amines
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US3443940A (en) * 1967-07-24 1969-05-13 Polaroid Corp Diffusion transfer employing ringclosure to release color-providing material for transfer
US3502472A (en) * 1965-10-11 1970-03-24 Agfa Gevaert Nv Development accelerators for silver halide emulsion layers
US3647436A (en) * 1970-08-31 1972-03-07 Eastman Kodak Co Developers for diffusion transfer film units
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US2191037A (en) * 1938-11-12 1940-02-20 Eastman Kodak Co Color forming developer containing amines
US2518698A (en) * 1948-11-18 1950-08-15 Eastman Kodak Co Chemical sensitization of photographic emulsions
GB904364A (en) 1956-03-07 1962-08-29 Kodak Ltd Improvements in photographic processes
US3128183A (en) * 1960-06-17 1964-04-07 Eastman Kodak Co Photographic halide emulsions sensitized with alkylene oxide polymers and aliphatic amines
US3128182A (en) * 1961-10-23 1964-04-07 Eastman Kodak Co Silver halide solvent containing developers and process
US3502472A (en) * 1965-10-11 1970-03-24 Agfa Gevaert Nv Development accelerators for silver halide emulsion layers
US3443940A (en) * 1967-07-24 1969-05-13 Polaroid Corp Diffusion transfer employing ringclosure to release color-providing material for transfer
US3647436A (en) * 1970-08-31 1972-03-07 Eastman Kodak Co Developers for diffusion transfer film units
US3749578A (en) * 1970-09-07 1973-07-31 Fuji Photo Film Co Ltd Image-receiving material for use in silver salt diffusion transfer photography

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4053312A (en) * 1974-09-04 1977-10-11 Eastman Kodak Company O-sulfonamidonaphthol diffusible dye image providing compounds
US4252894A (en) * 1975-10-22 1981-02-24 Gaf Corporation Hydrophilic color coupler composition containing diepoxide
US4186004A (en) * 1976-10-15 1980-01-29 Eastman Kodak Company Process of formation of color images, photographic product and treatment solutions useful therein
US4273863A (en) * 1977-09-29 1981-06-16 Eastman Kodak Company Process of formation of color images, photographic product and treating solutions useful for putting the process into practice
US4511643A (en) * 1982-09-22 1985-04-16 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic element
US4547452A (en) * 1982-09-29 1985-10-15 Fuji Photo Film Co., Ltd. Color diffusion transfer photographic element with sufinic acid
US4968588A (en) * 1986-01-30 1990-11-06 Fuji Photo Film Co., Ltd. Method for processing silver halide color photographic materials with a color developer comprising no benzyl alcohol and an accelerator

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